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No. 770,643. Patented September 20, 1904.

UNITED STATES PATENT @EEICE.

ERNST KLIE, OF CHARLOTTENBURG, GERMANY, ASSIGNOR TO THE FIRM OF CHEMISGH-TECHNISCHE FABRIK DR. ALB. R. W. BRAND U. (10., GESELLSCHAFT MITBESCHRAENKTER HAFTUNG.

PROCESS OF COLORING NATURAL CRYSTALLINE STONES.

SPECIFICATION forming part of Letters Patent No. 770,643, datedSeptember 20, 1904. Application filed April 20, 1904. $eria1No. 204,122.(No specimens.)

To all whom it y concern? 7 fatty acidsfor instance, of palmitic,stearic,

Be it known that I, ERNST KLIE, doctor of or oleic acid, the so-calledmetallic soaps 5 philosophy, a subject of the King of Prussia dissolvedin volatile oils containing free orand the German Emperor,residing at 3Gutenganic acids may be introduced into natural 5bergstrasse,Charlottenburg,GermanEmpire, crystalline stones, as naturalmarble, at the have invented new and useful Improvements ordinaryatmospheric pressure. If the stone in Processes of Coloring NaturalCrystalline thus treated is gently heated, the formation Stones, ofwhich the following is a specificaof colored precipitates will occur.The prestion. ent free organic acid will substitute the more I Thisinvention relates to the process of colweakfatty acid and form with themetal a oring natural crystalline stones, especially compound insolublein water. For instance, marble, by means of metallic soaps, and hasoleate of iron dissolved in turpentine-oil confor its object to enable amore complete coltaining acetic acid will give basic acetate of oring ofthe stone, even in its interior parts, iron when gently heated. Also thefollowing 15 and to render the process more expeditious reaction mayoccur: The organic acid introand considerably cheaper. duced into thestone by means of volatile oils If one wishes to color naturalcrystalline in which metallic soaps have been dissolved 5 stonescontaining carbonate of calciumfor combines itself with the metal of thesoap, and instance, natural marble-by means of introthe thus formedmetallic salt of the organic 2O ducing solutions of metallic soaps intothe acid reacts with the carbonate of calcium unstone, a reaction of themetallic soaps with the der formation of insoluble carbonates ofmetcarbonate will occur after a short time if a als and soluble organiccalcium salts. If one 7 relatively small amount of silicic acid ispreslixiviates the stones thus treated with water, ent in the stone, orafter a long time if a relthe formed precipitates will remain in the 5atively large amount of silicic acid is present stone and the solublecalcium salts will be rein the stone. As by the said reaction the colormoved from the stone. of the originally-introduced metallic soap is Myprocess consists in that I use metallic changed, it is necessary toeffect the reaction soaps of those metals the salts of which withbetween the stone and the metallic stone in as organic acids reacteasily with carbonate of 3 short time as possible. A ready reaction ofcalcium in presence of organic acids stronger carbonate of calcium withmetallic soaps may, than the fatty acids of the metallic soaps.,however,be caused only at high temperatures, For instance, I mayprepare a solution of by which a decomposition of the stone, espethirtyto forty parts, by weight, oleate of cially marble, to be colored iscaused, thus that copper in one hundred parts, by weight, of 35 theopalescent properties, the structure, the turpentine-oil and add to thesaid solution stability, and the splendor of the stone will be fiveparts, by weight, of acetic acid, which is injured. It is practicallyimpossible to polnearly that amount of acetic acid required for 5 ish astone thus treated or to work it with ina complete decomposition of theoleate of struments. copper, according to the formula: 0 The ob'ect ofthis in en ion is to meet the 4 J V t (C1sH33O2)2011+2C2H4O2 SELIClIlCOIlVGIllQIICGS; Oleate of copper. Acetic acid. The new process 1sbased on the new obser- 2(l1 TI34 O2+Cu(C2H3O2) 9 vat1on that organicacids, especially acetic 0161C ggmg acid, when dissolved in volatileoilsfor in- 45 stance, turpentine-oiL-does not decompose I have foundthat the presence of free ormarble or affect it injuriously, but can bein- ,ganic acid-for instance, acetic acid-effects troduced into thestone commonly with the that the metallic soap-for instance, oleate ofsaid oils. I have found that metallic salts of iron is more soluble inturpentine-oil than without the said addition.

I may use the soaps of those metals that form colored carbonates or givewith organic acids colored precipitates insoluble in water. The skilledWorkman will select the compounds suitable for his purposes, accordingto the value of the substances and the color desired.

I may carry out the coloring of the stone in the following manner: 1 drythe natural marble thus that it is practically free from water, placethe dried stone into the solution of the metallic soaps inturpentine-oil with acetic acid, and heat the solution to temperaturesbetween 50 and 70 centigrade. Then I take the stone from the solution,heat it in order to volatilize the solvent and lixiviate it with water.Thereupon I may dry the stone and finish it by treating withinstruments.

What I claim as my invention, and desire to secure by Letters Patent, is

l. The process of coloring natural crystalline stones containingcarbonate of calcium which consists in drying the stone, placing it intoa solution of metallic soaps in volatileoil and organic acids strongerthan the fatty acids of the metallic soaps and heating the saidsolution.

2. The process of coloring natural crystalline stones containingcarbonate of calcium which consists in drying the stone, placing it intoa solution of metallic oleate in turpentine-oil and acetic acid andheating the said solution.

In witness whereof I have hereunto signed my name, this 7th day ofApril, 1904, in the presence of two subscribing witnesses.

ERNST KLIE.

Witnesses:

. WOLDEMAR HAUPT,

HENRY HASPER.

